Self-sinking and air permeable plastic material

ABSTRACT

A composition comprising: a polyvinyl chloride resin; a first rubber component; a second rubber component; at least one copolymer; at least one low temperature plasticizer; at least one filler comprising calcium carbonate; at least one heat stabilizer; at least one internal lubricant; at least one antioxidant; and at least one biofouling agent.

FIELD OF THE INVENTION

The present invention is in the field of PVC (polyvinyl chloride)compositions. More particularly, it relates to PVC and nitrile rubberblends with low viscosities and low melting points comprising a varyingamount of filler. In particular, the disclosure pertains to PVCcompositions useful with producing a self-sinking plastic material thatwhen extruded into a tube will diffuse air evenly along its entirelength.

BACKGROUND OF THE DISCLOSURE

Aquatic pools, fishponds, sewage lagoons, wastewater treatment and/orfishing farms usually requires aeration devices to maintain theconcentration of dissolved oxygen, which is necessary for aquaticunderwater organisms and microorganisms, the stabilization of waterquality, and the ecological balance of aquatic pools. Microorganismsrequire the absorption of dissolved oxygen from the water to decomposethe redundant organic material and to perform nitrification and lowertoxicities. The mixing of small air bubbles and water increases theconcentration of dissolved oxygen of the pool water and promotes thedecomposition rate of the organic materials by microorganisms.

Aeration systems and tubes can provide major increases in the oxygenconcentration in a given water body. Current porous aeration tubes onthe market today employ heavy loads that cause the tubes to sink to thebottom of an aquatic pool. There are additional disadvantages thatinclude: weak aerobic capacity, easily clogged pores, and subsequentlywater that cannot easily be discharged.

Pollution and the preservation of water resources is a major globalconcern, but in some water body it is often difficult to provideaeration at the bottom and cumbersome and expensive installation methodsgreatly reduces the likelihood of widespread implementation. Therefore,in view of these limitations there is a need for improved aerationsystems and tubing for oxygenation of a given water body.

SUMMARY OF THE INVENTION

A composition comprising: a polyvinyl chloride resin; a first rubbercomponent; a second rubber component; at least one copolymer; at leastone low temperature plasticizer; at least one filler comprising calciumcarbonate; at least one heat stabilizer; at least one internallubricant; at least one antioxidant; and at least one biofouling agent.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The following is a detailed description of certain specific embodimentsof the self-sinking PVC tubing compositions disclosed herein.

Definitions

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that can vary depending upon thedesired properties sought to be obtained. It is noted that, as used inthis specification and the appended claims, the singular forms “a,”“an,” and “the,” include plural references unless expressly andunequivocally limited to one referent. As used herein, the term“include” and its grammatical variants are intended to be non-limiting,such that recitation of items in a list is not to the exclusion of otherlike items that can be substituted or added to the listed items. As usedherein, the term “comprising” means including elements or steps that areidentified following that term, but any such elements or steps are notexhaustive, and an embodiment can include other elements or steps.

Introduction

In one aspect, disclosed herein are compositions comprising: a polyvinylchloride resin; a first rubber component; a second rubber component; atleast one copolymer; at least one low temperature plasticizer; at leastone filler comprising calcium carbonate; at least one heat stabilizer;at least one internal lubricant; at least one antioxidant; and at leastone biofouling agent.

In some embodiments, the polyvinyl chloride resin comprises a PVC/VA(polyvinyl chloride/polyvinyl acetate copolymer) with an inherentviscosity of between about 0.5 to 0.9 and a K-value of between about 56to 64.

In some embodiments, the first rubber component is present in an amountbetween about 5 to 25 parts per hundred parts of resin.

In some embodiments, the second rubber component is present in an amountbetween about 30 to 50 parts per hundred parts of resin.

In some embodiments, the copolymer comprises at least one ethylenecopolymer.

In some embodiments, the low temperature plasticizer comprises di-octyladipate, Tris-2-Ethylhexyl-Trimellitate or combinations thereof.

In some embodiments, the calcium carbonate is present in an amountbetween about 120 to 300 parts per hundred parts of resin.

In some embodiments, the polyvinyl chloride resin comprises a PVC/VAwith an inherent viscosity of between about 0.7 to 0.8 and a K-value ofbetween about 59 to 62.

In some embodiments, the first rubber component comprises an amount ofNBR between about 10 to 20 parts per hundred parts of resin.

In some embodiments, the second rubber component comprises an amount of15 to 115 mesh crumbed tire between about 30 to 50 parts per hundredparts of resin.

In some embodiments, the copolymer comprises an amount of ethylene-vinylacetate between about 10 to 40 parts per hundred parts of resin.

In some embodiments, the low temperature plasticizer comprises an amountof di-octyl adipate between about 45 to 55 parts per hundred parts ofresin, an amount of Tris-2-Ethylhexyl-Trimellitate between about 45 to55 parts per hundred parts of resin or a combinations thereof.

In some embodiments, the calcium carbonate is present in an amountbetween about 140 to 280 parts per hundred parts of resin.

In some embodiments, the at least one heat stabilizer comprising anamount of calcium stearate between about 1 to 4 parts per hundred partsof resin, an amount of zinc stearate between about 1 to 4 parts perhundred parts of resin or a combinations thereof.

In some embodiments, the at least one internal lubricant is present inan amount between about 0.01 to 0.05 parts per hundred parts of resin.

In some embodiments, the at least one antioxidant is present in anamount between about 0.005 to 0.075 parts per hundred parts of resin.

In some embodiments, the at least one biofouling agent is selected fromthe group consisting of glycine betaine, sulfobetaine, titanium dioxidenanotubes or combinations thereof.

In some embodiments, the composition comprises a) the polyvinyl chlorideresin comprises a PVC/VA with an inherent viscosity of between about 0.7to 0.8 and a K-value of between about 59 to 62; b) the first rubbercomponent comprises an amount of NBR between about 12 to 18 parts perhundred parts of resin; c) the second rubber component comprises anamount of 20 to 110 mesh crumbed tire between about 35 to 45 parts perhundred parts of resin; d) the copolymer comprises an amount of ofethylene-vinyl acetate between about 15 to 35 parts per hundred parts ofresin; e) the low temperature plasticizer comprises an amount ofdi-octyl adipate between about 45 to 55 parts per hundred parts ofresin, an amount of Tris-2-Ethylhexyl-Trimellitate between about 45 to55 parts per hundred parts of resin or a combination thereof; d) thecalcium carbonate is present in an amount between about 140 to 280 partsper hundred parts of resin; e) the at least one heat stabilizercomprising an amount of calcium stearate between about 1 to 4 parts perhundred parts of resin, an amount of zinc stearate between about 1 to 4parts per hundred parts of resin or a combination thereof; f) the atleast one internal lubricant is present in an amount between about 0.01to 0.05 parts per hundred parts of resin; and g) the at least oneantioxidant is present in an amount between about 0.005 to 0.075 partsper hundred parts of resin, wherein the at least one biofouling agent isselected from an amount of glycine betaine between about 0.02 to 0.03parts per hundred parts of resin, an amount of sulfobetaine betweenabout 0.02 to 0.03 parts per hundred parts of resin, an amount oftitanium dioxide nanotubes between about 0.04 to 0.06 parts per hundredparts of resin or combinations thereof.

In some embodiments, the composition comprises a) the polyvinyl chlorideresin comprises a PVC/VA with an inherent viscosity of between about 0.7to 0.8 and a K-value of between about 59 to 62; b) the first rubbercomponent comprises an amount of NBR between about 12 to 18 parts perhundred parts of resin; c) the second rubber component comprises anamount of 20 to 110 mesh crumbed tire between about 35 to 45 parts perhundred parts of resin; d) the copolymer comprises an amount ofethylene-vinyl acetate between about 15 to 35 parts per hundred parts ofresin; e) the low temperature plasticizer comprises an amount ofdi-octyl adipate between about 45 to 55 parts per hundred parts ofresin, an amount of Tris-2-Ethylhexyl-Trimellitate parts per hundredparts of resin or a combination thereof; e) the calcium carbonate ispresent in an amount of about 218 parts per hundred parts of resin,144.7 parts per hundred parts of resin, 248 parts per hundred parts ofresin, 254 parts per hundred parts of resin or 260 parts per hundredparts of resin; f) the at least one heat stabilizer comprising an amountof calcium stearate between about 1 to 4 parts per hundred parts ofresin, an amount of zinc stearate between about 1 to 4 parts per hundredparts of resin or a combination thereof; g) the at least one internallubricant is present in an amount between about 0.01 to 0.05 parts perhundred parts of resin; and h) the at least one antioxidant is presentin an amount between about 0.005 to 0.075 parts per hundred parts ofresin, wherein the at least one biofouling agent is selected from anamount of glycine betaine between about 0.02 to 0.03 parts per hundredparts of resin, an amount of sulfobetaine between about 0.02 to 0.03parts per hundred parts of resin, an amount of titanium dioxidenanotubes between about 0.04 to 0.06 parts per hundred parts of resin orcombinations thereof.

In some embodiments, the composition comprises a) the polyvinyl chlorideresin comprises PVC/VA (polyvinylchloride/polyvinyl acetate copolymer)with an inherent viscosity of about 0.787, and a K-value of about 60.9;b) the first rubber component comprises an amount of NBR of about 15parts per hundred parts of resin; b) the second rubber componentcomprises an amount of 20 to 110 mesh crumbed tire of about 40 parts perhundred parts of resin; c) the copolymer comprises an amount ofethylene-vinyl acetate of about 25 parts per hundred parts of resin; d)the low temperature plasticizer comprises an amount of di-octyl adipateof about 50 parts per hundred parts of resin and an amount ofTris-2-Ethylhexyl-Trimellitate of about 50 parts per hundred parts ofresin; e) the calcium carbonate is present in an amount of about 218parts per hundred parts of resin, 144.7 parts per hundred parts ofresin, 248 parts per hundred parts of resin, 254 parts per hundred partsof resin or 260 parts per hundred parts of resin; f) the at least oneheat stabilizer comprises an amount of calcium stearate of about 3 partsper hundred parts of resin and an amount of zinc stearate of about 3parts per hundred parts of resin; g) the at least one internal lubricantcomprises an amount of stearic acid of about 0.03 parts per hundredparts of resin; h) the at least one antioxidant comprises an amount ofADK STAB AO-50 (Octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) of about 0.025 partsper hundred parts of resin; and wherein the at least one biofoulingagent comprises an amount of glycine betaine of about 0.025 parts perhundred parts of resin, an amount of sulfobetaine of about 0.025 partsper hundred parts of resin and an amount of titanium dioxide nanotubesof about 0.05 parts per hundred parts of resin.

Polyvinylchloride

PVC (Polyvinyl chloride) resin has a combination of properties whichmake it particularly suitable for use as a structural material. Inapplications in which impact strength of the structural plastic isimportant, the PVC can be formulated with impact-modifier resins whichimprove the impact strength of the resulting composition. Such highimpact-strength PVC compositions can be readily extruded or otherwiseformed into a variety of articles which have excellent impact strength,toughness and other desired mechanical and chemical properties.

The PVC constituent can comprise a mixture of a homopolymer and one ormore copolymers of vinyl chloride and/or chlorinated PVC or a mixture oftwo or more copolymers of vinyl chloride and/or chlorinated PVC. In thedisclosure herein, the PVC component can be copolymer of vinyl chlorideand one or more other monomers, for example, VA (vinyl acetate) and thelike, vinylidene halides such as vinylidene chloride, alkyl esters ofcarboxylic acids such as acrylic acid, ethyl acrylate, 2-ethylhexylacrylate and the like, unsaturated hydrocarbons such as ethylene,propylene, isobutylene and the like, allyl compounds such as allylacetate and the like. In the use of a copolymer of vinyl chloride, it ispreferred that the vinyl chloride content comprise at least about 80 wt% of the copolymer. In some embodiments, the PVC constituent of thecomposition of the present invention comprises a copolymer of vinylchloride with VA, particularly a copolymer having a K-value of fromabout 56 to 64, most preferably from about 59 to 62.

Stabilizers for PVC

Polymers and copolymers of PVC and vinyl acetate can be sensitive toheat. For this reason, heat stabilizers are usually added to prevent thepolymers from decomposing during normal processing.

The term “stabilizer” as used herein shall mean one or more organic orinorganic compounds useful for protection of PVC against thermal,ultraviolet light, and/or mechanical degradation. The stabilizer mayenhance the effect of the stabilizer system for the PVC and/or act as anantioxidant or stabilizer for the NBR rubber as well. Examples ofconventional stabilizers are disclosed in the Kirk-Othmer Encyclopediaof Chemical Technology, “Heat Stabilizers”, vol 12, pages 1071-91 (JohnWiley, NY 1994), incorporated herein by reference, and is not intendedto be limiting to the disclosure herein.

Stabilizers may include organotin compounds such as alkyltin,dialkyltin, aryltin, poly(dialkyltin maleate), dialkyltin bis(alkylmaleate), dialkyltin bis(2-alkylthioglycolate), where the alkyl group isC₄-C₈. Some stabilizers contain calcium, zinc, magnesium, lead, bariumand cadmium salts or soaps. In some embodiments, the stabilizer iscomprised of combinations of Ca—Zn, Ba—Ca—Zn and Ba—Zn. Moreover,mixtures of alkaline earth metal salts and polyhydric alcohols.Combinations of aluminum salts and calcium salts may also be used asstabilizer components.

Additional stabilizer components may include epoxy compounds,antioxidants (i.e. phenols or amines), polyols, phosphites, β-diketones,substituted amines and hydrotalcite. NBR rubbers typically utilizestabilizer systems including antioxidants of many classes (phenolic,amines and phosphites). Additional examples include sodium oleate,calcium stearate, zinc stearate, dioctyl phthalate, BHT (butylatedhydroxy toluene), ESO (epoxidized soybean oil), and a variety ofbarium-zinc salt compounds. In some embodiments, each stabilizer may bepresent in levels of about 0.01 to about 15.0, preferably about 0.5 toabout 8.0, more preferably 2.0 to 4.0 parts per hundred parts ofpolyvinyl chloride resin. The levels of usage of the stabilizer vary bythe chemical identity the active ingredient and by the number ofstabilizers present in any stabilizer package.

Acrylonitrile-Butadiene Rubbers (NBR)

NBR (Acrylonitrile-Butadiene Rubber) may be classified by theInternational Institute of Synthetic Rubber Producers (IISRP). NBR iscomprised of unsaturated copolymers of 2-propenenitrile and variousbutadiene monomers (1,2-butadiene and 1,3-butadiene). In some instances,these elastomers contain acrylonitrile to butadiene amounts of about 25wt % to 50 wt %, 28 wt % to 39 wt % or 30 wt % to 35 wt % acrylonitrile.The disclosure herein pertains to a nitrile polymer blend comprised ofacrylonitrile-butadiene copolymer blended with a PVC resin.

Crumb Rubber

The term “Crumb rubber” relates to a rubber material derived by reducingscrap tire or other rubber into uniform granules with the inherentlyreinforcing materials, such as steel and fiber removed along with anyother type of inert contaminants such as dust, glass, or rocks. Thecrumb rubber can include particles of reclaimed rubber. Reclaimed rubbercan be recycled rubber, which can be derived from synthetic and/ornatural rubbers or plastics. In embodiments, the crumb rubber can bemade of 100 percent recycled tires. At least a portion of the particlesof reclaimed rubber can be passed through a series of mesh sieves beforethe crumb rubber is incorporated into the rubber composition. Forexample, from 10 percent to 50 percent of the particles of reclaimedrubber can be passed through a 30 to 100 mesh or other mesh sieve.

Biofouling Agents

The main sources of fouling in a given water body can be the result ofsediments (i.e., scale, silt, algae and sludge), corrosion and bacterialactivity. Lack of knowledge of aeration systems and equipment, taxonomyand ecology of tropical fouling organisms is a major stumbling block todevelopment of effective systems for antifouling management.

Chemical fouling inhibitors can reduce fouling in many systems, mainlyby interfering with the crystallization, attachment, or consolidationsteps of the fouling process. Examples for water systems are: chelatingagents, such as EDTA, long-chain aliphatic amines or polyamines, such asoctadecylamine, helamin, and other suitable amines, organic phosphonicacids, such as etidronic acid, or polyelectrolytes, such as polyacrylicacid and polymethacrylic acid.

Non-toxic anti-fouling coatings or embedded components are hydrophiliccoatings. These coatings or embedded components rely on hydrationwhereby the substitution of water for proteins and microorganisms isminimized. Some examples without limiting the disclosure herein arecoatings based on hydrated zwitterions, such as glycine betaine andsulfobetaine. These coatings or embedded components prevent bacteriaattachment and biofilm formation.

The ability of carbon nanotubes (CNTs) to undergo surface modificationallows them to form nanocomposites (NCs) with materials such aspolymers, metal nanoparticles, biomolecules and metal oxides. Thebiocidal nature, protein fouling resistance, and fouling releaseproperties of CNT-NCs render them the perfect material for biofoulingprevention.

The disclosure herein employs at least one biofouling agent is selectedfrom the group consisting of glycine betaine, sulfobetaine, titaniumdioxide nanotubes or combinations thereof, wherein the biofouling agentis mixed with the self-sinking PVC tubing compositions described herein.Therefore, the biofouling agent is embedded at the surface of the tubingafter further compounding using melt extrusion whereby the compositionis formed into any desired shape (i.e., tubing).

Furthermore, fouling can be reduced by maintaining a relatively highfluid velocity throughout the aeration tubing.

Compounding

During the compounding process the PVC resin is combined with a othercomponents, including heat stabilizers, lubricants and plasticizers.Additional additives may include fillers, antioxidants, etc. Additivesmay influence or determine mechanical properties, UV light and thermalstability, etc. In the compounding process, the additives are mixed withthe PVC resin. In one embodiment, the compounding method employs ahigh-speed mixer that thoroughly blends all the components. The resultis a semi-dry to dry powder, which may be fed into processing equipment.

The blends obtained from the mixing process can be further compoundedwith a mixer such as a Banbury batch mixer, a Farrel Continuous Mixer ora single or twin screw extruder. In some embodiments, the semi-dry todry blend may be mixed using a Brabender mixer, a Henschel mixer or aribbon blender. In some embodiments, the semi-dry to dry blend may befurther compounded using melt extrusion and formed into any desiredshape (i.e., pellet, tubing, etc.).

EXAMPLES

The powdered PVC/VA (polyvinyl chloride/polyvinyl acetate copolymer,ethyl-vinyl acetate copolymer were placed in a high intensity 500 LHenschel dry powder mixer along with the stabilizers. The PVC/VA andstabilizers calcium stearate and zinc stearate were mixed withsufficient shear to raise the temperature of the coated PVC to at leastabout 80° C.

Then, the TOTM (Tris-2-Ethylhexyl-Trimellitate) and DOA (di-octyladipate) were added to the PVC/VA in the mixer and the temperaturelowers for about 5 minutes from about 80° C. to about 60° C. During thistime the TOTM and DOA are absorbed the mixture forms a dry to wetpowder.

After about 8 to 10 minutes the NBR rubber and meshed tire were blendedwith the PVC/VA as well as the remaining components including thefiller, stearic acid, antioxidant (ADK STAB AO-50) and biofouling agents(glycine betaine, sulfobetaine, titanium dioxide nanotubes). Then, themixture was intimately blended and after about 5 minutes the temperaturelowers to about 40° C. At this time, the mixture was added to a 1000 Lcooler mixer and the mixture was allowed to cool to room temperature.

The mixture was transferred from the cooler mixture and fluxed throughan extruder with a first zone temperature of about 175° C., asecond/third zone temperature of 145° C. and a fourth zone temperatureof 120° C. to yield blends showing good physical properties. Duringextrusion the blend is passed through a die with a blade that cuts thepelletized material to form pellets with a diameter of about 5 mm and alength of about 3 mm. The, a cooling system cools the pellets from about125° C. to room temperature. Table 1 shows the components and relativeparts-per-hundred amounts used to prepare Examples 1A-1E.

TABLE 1 Formulations 1A-1E PHR (Parts per Hundred Resin) ComponentsDescription 1A 1B 1C 1D 1E NBR Buna- 15 15 15 15 15 N, Perbunan,acrylonitrile butadiene rubber CRUMBED 30-100 Mesh 40 40 40 40 40 TIREPVC/VA PVC/VA Copolymer 100 100 100 100 100 resins, Inherent viscosity =0.787, K- value = 60.9 EVA742 Ethylene-vinyl acetate 25 25 25 25 25 DOADi-octyl adipate low 50 50 50 50 50 temperature plasticizer TOTMTris-2-Ethylhexyl- 50 50 50 50 50 Trimellitate Calcium Filler 218 144.7248 254 260 Carbonate Calcium Heat stabilizer 3 3 3 3 3 stearate Zincstearate Heat stabilizer 3 3 3 3 3 stearic acid Internal Lubricant 0.030.03 0.03 0.03 0.03 ADK STAB Antioxidant 0.025 0.025 0.025 0.025 0.025AO-50 Glycine Biofouling agent 0.025 0.025 0.025 0.025 0.025 betaineSulfobetaine Biofouling agent 0.025 0.025 0.025 0.025 0.025 TNTBiofouling agent 0.05 0.05 0.05 0.05 0.05Properties and Applications

The compositions disclosed herein are useful to produce highlyenvironmentally resistant yet flexible plastic aeration tubing that isself-sinking, non-kinking and holds no memory when deployed. Theself-sinking property of the tubing is attributed to the compositiondisclosed herein and in particular, the amount and type of filler arepredetermined depending on the inner diameter and outer diameter of thetube, the depth of the body of water and the type of application site(i.e., fish farm, harbor and an environmental treatment facility, etc.).

For example, at a fish or shrimp farming application site the depth maybe about 2 m to 3 m to the bottom of the body of water. In someembodiments, the amount and type of filler and the inner diameter andouter diameter of the tube are selected to have a specific gravitysuitable for a surface water and/or environmental treatment at a depthof about 5 m. In some embodiments, the amount and type of filler and theinner diameter and outer diameter of the tube are selected to have aspecific gravity suitable for deicing of a lake or pond at a depth ofabout 15 m. In some embodiments, the amount and type of filler and theinner diameter and outer diameter of the tube are selected to have aspecific gravity suitable for a surface water aeration of a body ofwater with a large surface area at a depth of about 20 m and a length ofabout 10 km or less. In some embodiments, the amount and type of fillerand the inner diameter and outer diameter of the tube are selected tohave a specific gravity suitable for agitation to create a bubblecurtain and/or bubble barrier in a harbor at a depth of about 100 m.Therefore, as the outer diameter increases the volume of the tube andthe wall thickness both increase. As such, the addition of more or lessfiller with the disclosed compositions is needed to produce a tube withthe desired specific gravity, which enables the tube to sink to anappropriate depth at a specific application site.

There is no restriction on the length of the tube, and the tubing can bemanufactured to cover a very large surface area. Compressed air entersthe tubing creating an inner pressure along both sides of the entirelength of tubing and allows the compressed air to release through aporous surface in the tubing, creating efficient micro-bubbles thatprevent clogging and fowling, along the entire length of the tubing. Thereleased air from the porous surface forms a bubble curtain of uniformand evenly dispersed fine bubbles that optimize the oxygen transfer, andlift water which aids in complete circulation throughout the watercolumn surrounding the tube.

Since the tubing operates without moving parts or electrical componentsin the body of water at the application sire, the performance andefficiency is improved and with significantly reduced electrical andmaintenance related costs in comparison to other aeration systems.

For deicing purposes, the air bubbles leaving the tubing also bringdense, heavier, warmer water from the depths of the body of water to thesurface, which results in efficient inhibition of ice formation.

Additional properties derived from tubing manufactured from thedisclosed compositions include but are not limited to strong physicalproperties such as high tensile strength, modulus and elongation; waterproof and/or hydrophobic when the tubing is not in operation; flexibleand is easy to install and is safe for the environment (i.e., does notcontain lead); high oxygen transfer rate; highly resistant plasticmaterial (i.e., chemicals, salinity, temperature).

In some embodiments, the tubing derived from the disclosed compositionshas applications ranging from farm ponds and industrial projects and issuitable for fresh and salt water applications in shallow and deepbodies of water. Other applications include but are limited tocommercial, government and private applications; aeration sewagelagoons; wastewater treatment process plants; leachate ponds; earthenponds, dugouts and lakes, etc.; waterways and channels; storm waterretention ponds; septic systems; aquaculture; deicing docks, power plantwater intake, marina slips, shoreline and/or water retention structures,industrial ship docking, ocean freight & Maritime transport, pumpingoperations and nuclear power generating plants; efficient bottom-to-topwater circulation and mixing for water treatment, deicing, and otherrelated applications; pathogen reduction, whereby the bubbles liftdeeper waters to the surface for UV exposure.

In some embodiments, the tubing derived from the disclosed compositionshas applications ranging from underwater air bubble curtains forprotecting fish and marine mammals from underwater blasting and piledriving noise; protecting marine mammals from offshore oil platforms andwind power farm construction and continuous operation vibrations andnoises (i.e., machinery and engine noise); containing oil spills in abody of water within a selected area; controlling the movement of marinelife, plants and debris. In some aspects, a bubble curtain and/or bubblebarrier can control the movement of marine life and floating debris andcontrol the migration of jellyfish, fish, seagrass, debris, sediments,etc. This may provide an improvement in water quality, including but notlimited to improved water clarity, reduction of algae and reduced H₂Sand odor suppression.

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications can be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

The present disclosure is not to be limited in terms of the particularembodiments described in this application. Many modifications andvariations can be made without departing from its spirit and scope, aswill be apparent to those skilled in the art. Functionally equivalentmethods and compositions within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds compositions or biologicalsystems, which can of course vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the like,include the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember.

All publications, patent applications, issued patents, and otherdocuments referred to in this specification are herein incorporated byreference as if each individual publication, patent application, issuedpatent, or other document was specifically and individually indicated tobe incorporated by reference in its entirety. Definitions that arecontained in text incorporated by reference are excluded to the extentthat they contradict definitions in this disclosure.

What is claimed is:
 1. A composition comprising: a polyvinyl chlorideresin; a first rubber component; a second rubber component; at least oneethylene copolymer; at least one low temperature plasticizer; at leastone filler comprising calcium carbonate; at least one heat stabilizer;at least one internal lubricant; at least one antioxidant; and at leastone biofouling agent.
 2. The composition of claim 1, wherein thepolyvinyl chloride resin comprises a PVC/VA (polyvinylchloride/polyvinyl acetate copolymer) with an inherent viscosity ofbetween about 0.5 to 0.9 and a K-value of between about 56 to
 64. 3. Thecomposition of claim 1, wherein the first rubber component is present inan amount between about 5 to 25 parts per hundred parts of resin.
 4. Thecomposition of claim 1, wherein the second rubber component is presentin an amount between about 30 to 50 parts per hundred parts of resin. 5.The composition of claim 1, wherein the low temperature plasticizercomprises di-octyl adipate, Tris-2-Ethylhexyl-Trimellitate orcombinations thereof.
 6. The composition of claim 1, wherein the calciumcarbonate is present in an amount between about 120 to 300 parts perhundred parts of resin.
 7. The composition of claim 1, wherein thepolyvinyl chloride resin comprises a PVC/VA with an inherent viscosityof between about 0.7 to 0.8 and a K-value of between about 59 to
 62. 8.The composition of claim 1, wherein the first rubber component comprisesan amount of NBR between about 10 to 20 parts per hundred parts ofresin.
 9. The composition of claim 1, wherein the second rubbercomponent comprises an amount of 15 to 115 mesh crumbed tire betweenabout 30 to 50 parts per hundred parts of resin.
 10. The composition ofclaim 1, wherein the copolymer comprises an amount of ethylene-vinylacetate between about 10 to 40 parts per hundred parts of resin.
 11. Thecomposition of claim 1, wherein the low temperature plasticizercomprises an amount of di-octyl adipate between about 45 to 55 parts perhundred parts of resin, an amount of Tris-2-Ethylhexyl-Trimellitatebetween about 45 to 55 parts per hundred parts of resin or acombinations thereof.
 12. The composition of claim 1, wherein thecalcium carbonate is present in an amount between about 140 to 280 partsper hundred parts of resin.
 13. The composition of claim 1, wherein theat least one heat stabilizer comprising an amount of calcium stearatebetween about 1 to 4 parts per hundred parts of resin, an amount of zincstearate between about 1 to 4 parts per hundred parts of resin or acombinations thereof.
 14. The composition of claim 1, wherein the atleast one internal lubricant is present in an amount between about 0.01to 0.05 parts per hundred parts of resin.
 15. The composition of claim1, wherein the at least one antioxidant is present in an amount betweenabout 0.005 to 0.075 parts per hundred parts of resin.
 16. Thecomposition of claim 1, wherein the at least one biofouling agent isselected from the group consisting of glycine betaine, sulfobetaine,titanium dioxide nanotubes or combinations thereof.
 17. The compositionof claim 1, comprising a) the polyvinyl chloride resin comprises aPVC/VA with an inherent viscosity of between about 0.7 to 0.8 and aK-value of between about 59 to 62; b) the first rubber componentcomprises an amount of NBR between about 12 to 18 parts per hundredparts of resin; c) the second rubber component comprises an amount of 20to 110 mesh crumbed tire between about 35 to 45 parts per hundred partsof resin; d) the copolymer comprises an amount of ethylene-vinyl acetatebetween about 15 to 35 parts per hundred parts of resin; e) the lowtemperature plasticizer comprises an amount of di-octyl adipate betweenabout 45 to 55 parts per hundred parts of resin, an amount ofTris-2-Ethylhexyl-Trimellitate between about 45 to 55 parts per hundredparts of resin or a combination thereof; f) the calcium carbonate ispresent in an amount between about 140 to 280 parts per hundred parts ofresin; g) the at least one heat stabilizer comprising an amount ofcalcium stearate between about 1 to 4 parts per hundred parts of resin,an amount of zinc stearate between about 1 to 4 parts per hundred partsof resin or a combination thereof; h) the at least one internallubricant is present in an amount between about 0.01 to 0.05 parts perhundred parts of resin; and i) the at least one antioxidant is presentin an amount between about 0.005 to 0.075 parts per hundred parts ofresin, wherein the at least one biofouling agent is selected from anamount of glycine betaine between about 0.02 to 0.03 parts per hundredparts of resin, an amount of sulfobetaine between about 0.02 to 0.03parts per hundred parts of resin, an amount of titanium dioxidenanotubes between about 0.04 to 0.06 parts per hundred parts of resin orcombinations thereof.
 18. The composition of claim 1, comprising a) thepolyvinyl chloride resin comprises a PVC/VA with an inherent viscosityof between about 0.7 to 0.8 and a K-value of between about 59 to 62; b)the first rubber component comprises an amount of NBR between about 12to 18 parts per hundred parts of resin; c) the second rubber componentcomprises an amount of 20 to 110 mesh crumbed tire between about 35 to45 parts per hundred parts of resin; d) the copolymer comprises anamount of ethylene-vinyl acetate between about 15 to 35 parts perhundred parts of resin; e) the low temperature plasticizer comprises anamount of di-octyl adipate between about 45 to 55 parts per hundredparts of resin, an amount of Tris-2-Ethylhexyl-Trimellitate parts perhundred parts of resin or a combination thereof; f) the calciumcarbonate is present in an amount of about 218 parts per hundred partsof resin, 144.7 parts per hundred parts of resin, 248 parts per hundredparts of resin, 254 parts per hundred parts of resin or 260 parts perhundred parts of resin; g) the at least one heat stabilizer comprisingan amount of calcium stearate between about 1 to 4 parts per hundredparts of resin, an amount of zinc stearate between about 1 to 4 partsper hundred parts of resin or a combination thereof; h) the at least oneinternal lubricant is present in an amount between about 0.01 to 0.05parts per hundred parts of resin; and i) the at least one antioxidant ispresent in an amount between about 0.005 to 0.075 parts per hundredparts of resin, wherein the at least one biofouling agent is selectedfrom an amount of glycine betaine between about 0.02 to 0.03 parts perhundred parts of resin, an amount of sulfobetaine between about 0.02 to0.03 parts per hundred parts of resin, an amount of titanium dioxidenanotubes between about 0.04 to 0.06 parts per hundred parts of resin orcombinations thereof.
 19. The composition of claim 1, comprising a) thepolyvinyl chloride resin comprises PVC/VA (polyvinyl chloride/polyvinylacetate copolymer) with an inherent viscosity of about 0.787, and aK-value of about 60.9; b) the first rubber component comprises an amountof NBR of about 15 parts per hundred parts of resin; c) the secondrubber component comprises an amount of 20 to 110 mesh crumbed tire ofabout 40 parts per hundred parts of resin; d) the copolymer comprises anamount of ethylene-vinyl acetate of about 25 parts per hundred parts ofresin; e) the low temperature plasticizer comprises an amount ofdi-octyl adipate of about 50 parts per hundred parts of resin and anamount of Tris-2-Ethylhexyl-Trimellitate of about 50 parts per hundredparts of resin; f) the calcium carbonate is present in an amount ofabout 218 parts per hundred parts of resin, 144.7 parts per hundredparts of resin, 248 parts per hundred parts of resin, 254 parts perhundred parts of resin or 260 parts per hundred parts of resin; g) theat least one heat stabilizer comprises an amount of calcium stearate ofabout 3 parts per hundred parts of resin and an amount of zinc stearateof about 3 parts per hundred parts of resin; h) the at least oneinternal lubricant comprises an amount of stearic acid of about 0.03parts per hundred parts of resin; i) the at least one antioxidantcomprises an amount of ADK STAB AO-50 (Octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) of about 0.025 partsper hundred parts of resin; and wherein the at least one biofoulingagent comprises an amount of glycine betaine of about 0.025 parts perhundred parts of resin, an amount of sulfobetaine of about 0.025 partsper hundred parts of resin and an amount of titanium dioxide nanotubesof about 0.05 parts per hundred parts of resin.